Explosives comprising modified copolymers of polyisobutylene and maleic anhydride as emulsifiers

ABSTRACT

The invention provides an explosive composition consisting of  
     A) an oxygen-donating constituent, which forms a disperse phase,  
     B) an organic constituent, which forms a dispersion phase, and  
     C) at least one emulsifier,  
     wherein the emulsifier includes a copolymer comprising, in random or regular order, structural units derived from maleic anhydride and from one or more olefins having more than 40 carbon atoms, where the structural units derived from maleic anhydride have been modified by reaction with alcohols, aminoalcohols, ammonia or amines.

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of German patent application198 47 868.2, filed Oct. 16, 1998, and U.S. patent application Ser. No.09/419,215, filed Oct. 15, 1999.

BACKGROUND OF THE INVENTION

[0002] Of the explosives used worldwide today, the ammonium nitrateexplosives are the largest group. They are widespread particularly inmining. A particularly important group within the ammonium nitrateexplosives in this connection are the emulsion explosives, which consistessentially of a water- (or salt)-in-oil emulsion of an aqueoussolution, supersaturated at room temperature, in an oil matrix (fuel).The oil phase is the continuous phase and includes small droplets of thesupersaturated solution of the oxidizing agent. In this connection, thewater content of the solution can be up to below 4% by weight. Thedissolved salts are metastable and have a tendency towardcrystallization. If, for example, ammonium nitrate crystals form, thishas unfavorable effects on the emulsion (solidification, the emulsion isno longer pumpable) and also on the cap sensitivity of the emulsion,i.e. the explosive becomes less sensitive to initial detonation. Inorder to keep such an emulsion stable, therefore, an emulsifier isgenerally required which is suitable for the preparation of water-in-oilemulsions. Because of its surface activity, it promotes emulsificationof the salt phase in small droplets and prevents coalescence of theformed droplets after the emulsion has formed.

[0003] The emulsion, also called matrix, is generally still notignitable, and therefore, in order to achieve sufficient capsensitivity, the density of the matrix must be lowered by addingmicrospheres (glass bubbles), by chemical gassing or by another method,such as, for example, by adding granular ammonium nitrate. The emulsionsare then in some circumstances also ignitable without boosters withblasting caps. Such emulsions are safety explosives. This technology wasdescribed for the first time in U.S. Pat. No. 3,447,978.

[0004] U.S. Pat. No. 3,447,978 discloses explosive emulsions consistingof a salt-in-oil emulsion of a supersaturated ammonium nitrate solutionin an oil matrix, an emulsifier of the water-in-oil type, e.g. asorbitan ester, fatty acid glycerides or phosphoric esters, being usedas emulsifiers. These emulsifiers, however, only give emulsions with lowlong-term stability.

[0005] EP-A-0 155 800 discloses emulsion explosive material mixtureswhich comprise emulsifiers, where at least one emulsifier is stronglylipophilic and an agent for altering the electrical conductivity of theemulsion, which essentially consists of a lipophilic and of ahydrophilic component, and in which the lipophilic constituent has achain structure derived from a polymer of a monoolefin containing 3-6carbon atoms. In particular, reaction products ofpoly(isobutenyl)succinic anhydride with aminoalcohols, amines andsorbitol as emulsifiers are described.

[0006] EP-A-0 285 608 discloses water-in-oil emulsions, where theemulsifiers present are reaction products of a hydrocarbon-substitutedcarboxylic acid or a hydrocarbon-substituted anhydride (or an ester oramide derived therefrom) with ammonia or at least one amine, thehydrocarbon radical having on average 20-500 carbon atoms. Polymerscontaining two or more hydrocarbon radicals are not disclosed. Reactionproducts of poly(isobutenyl)succinic anhydrides with morpholine andaminoalcohols are specifically described.

[0007] The emulsifiers cited in EP-A-0 155 800 and EP-A-0 285 608 andbased on polyisobutenylsuccinic anhydride (i.e. the reaction product ofa long-chain, branched olefin with maleic anhydride), produce, incontrast to the emulsifiers of the first generation cited in U.S. Pat.No. 3,447,978, emulsions with high long-term stability. The baseemulsifiers, however, have the disadvantage that their synthesis,because of the underlying ene reaction, requires very high temperatures(180-230° C.) and relatively long reaction times, which leads to a highconsumption of energy and correspondingly high preparation costs.

[0008] Polymers of polyisobutylene and maleic anhydride are also part ofthe prior art.

[0009] WO-A-90/03359 discloses polymers of polyisobutylene and maleicanhydride which, after they have been functionalized using polyamines,can be used as additives in fuels and lubricating oils. EP-A-0 831 104discloses terpolymers of polyisobutylene, α-olefins and maleic anhydrideand also reaction products of these terpolymers with polyamines foranalogous applications.

SUMMARY OF THE INVENTION

[0010] Surprisingly, we have now found that not only derivatives ofmonomeric adducts of polyisobutylene and maleic anhydride, but alsoderivatives of polymeric adducts of maleic anhydride and olefins having20-500 carbon atoms, alone or mixed with other emulsifiers, are suitableas extremely effective emulsifiers for emulsion explosives. In contrastto the compounds cited in EP-A-0 155 800 and EP-A-0 285 608, thesecompounds have two or more hydrophobic groups and two or morehydrophilic head groups on the polymer backbone. The parent polymericanhydrides can be prepared at a significantly lower temperature (80-150°C.) and by free-radical copolymerization significantly more quickly thanthe alkenylsuccinic acid derivatives of the prior art, meaning that theyhave ecological and also economic advantages over the prior art.Surprisingly, despite having molecular weights which are significantlyhigher than those of polyisobutenylsuccinic acid derivatives, theproducts do not have increased viscosities, meaning that the productscan be handled without problems despite the relatively high molecularweight. In this connection, the emulsifying action and emulsionstability of the products, particularly in mixtures with small amountsof coemulsifiers, correspond to at least those of the products cited inthe prior art.

[0011] The invention thus provides an explosive composition consistingof

[0012] A) an oxygen-donating constituent, which forms a disperse phase,

[0013] B) an organic constituent, which forms a dispersion phase, and

[0014] C) at least one emulsifier,

[0015] wherein the emulsifier includes a copolymer comprising, in randomor regular order, structural units derived from maleic anhydride andfrom one or more olefins having more than 40 carbon atoms, where thestructural units derived from maleic anhydride have been modified byreaction with alcohols, aminoalcohols, ammonia or amines.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0016] In the text below, the term “maleic anhydride” also refers to themaleic anhydride modified in the sense given above by reaction withalcohols, aminoalcohols, ammonia or amines.

[0017] The emulsifier according to the invention comprises, in thecopolymer chain, at least one olefin, preferably an α-olefin having morethan 40, preferably from 40 to 500, in particular from 40 to 200, carbonatoms. The copolymer may also further comprise other comonomers.

[0018] Suitable olefins for the preparation of the polymers according tothe invention are olefins preferably containing a double bond in theα-position or mixtures of the number of such olefins. Particularpreference is given to olefins obtained by polymerization ofC₂-C₆-monoolefins, such as, for example, polypropylenes orpolyisobutylenes in the molecular weight range from, preferably,200-5000 g/mol, and which comprise >30%, preferably >50%, particularlypreferably >70%, of isomers containing a double bond in the α-position,i.e., for example, containing an end group R—C(═CH₂)CH₃. Suchpolyisobutylene grades are obtainable, for example, under the tradenames Glissopal® or Ultravis®. In this connection, particularly suitablepolyisobutylenes are those which have a high content of isomerscontaining an α-position double bond. Particularly suitable as olefincomponents are also mixtures of polyisobutylenes and straight-chain orbranched-chain C₁₀-C₃₀-α-olefins or mixtures of polyisobutylenes withalkylallyl polyglycol ethers having from 3 to 20 ethylene oxide units.In this case terpolymers of polyisobutylene, maleic anhydride andα-olefin or allylmethyl polyglycol ethers. form. The alkylallylpolyglycol ethers mentioned are preferably allylmethyl polyglycol ethersin the molecular weight range from 200 to 1000 g/mol.

[0019] The emulsifiers according to the invention can be synthesized bymethods known per se, one description being, for example, in Oil GasEuropean Magazine 1996, 22, 38-40. Firstly, olefins, preferablyα-olefins, particularly preferably polyisobutylene or mixtures ofpolyisobutylene and short-chain C₁₀-C₃₀-α-olefins or mixtures ofpolyisobutylene with allylalkyl polyglycol ethers and maleic anhydrideare polymerized using a suitable free-radical initiator. The molarquantity ratio between maleic anhydride and the total of the othercomonomers is preferably from 0.7:1 to 1.6:1. The polymerization can becarried out without a diluent, or also in a nonprotic solvent. Thereaction temperature of the polymerization is between 50 and 200° C.,preferably between 80 and 160° C. Alternating copolymers of olefin andmaleic anhydride preferably form. In the second reaction step, theresulting polymer is reacted in a polymer-analogous reaction withalcohols or aminoalcohols to give polymeric half-esters, with ammoniaand/or amines and, where appropriate, also with aminoalcohols, to givepolymeric half-amides or imides.

[0020] Suitable alcohols for the functionalization of the maleicanhydride copolymers to give half-esters are monoalcohols having 1-6carbon atoms, e.g. methanol, ethanol, propanols, butanols or pentanols;alkylpolyglycols are also suitable.

[0021] Suitable aminoalcohols are, for example,N,N-dimethylaminoethanol, N,N-diethylaminoethanol,N,N-dibutylaminoethanol, 3-dimethylaminopropanol,N-hydroxyethylmorpholine, monoethanolamine, diethanolamine,triethanolamine, 3-aminopropanol, isopropanolamine and2-(2-aminoethoxy)ethanol. The half-ester formation is carried out at 30to 150° C., preferably at 50 to 100° C. In order to avoid crosslinkingreactions, aminoalcohols with a tertiary amine nitrogen and a hydroxylfunction, such as dimethylaminoethanol, diethylaminoethanol orN-hydroxyethylmorpholine, are particularly preferred.

[0022] Suitable amines for the functionalization of the maleic anhydridecopolymers are monoamines with a primary or secondary amino function,such as methylamine, ethylamine, butylamine, laurylamine, coconut fattyamine, stearylamine, dimethylamine, diethylamine, dibutylamine etc., butalso di- and polyamines, e.g. 3-dimethylaminopropylamine,3-diethyl-aminopropylamine or 3-morpholinopropylamine.

[0023] Preferred amines contain only one condensable alcohol or aminogroup in order to prevent crosslinking of the individual polymer units.Using the amines listed, olefin/MA copolymers (MA maleic anhydride)functionalized to the half-amide are obtained at reaction temperaturesof at most 50-60° C. Above 50° C., imide formation arises to anincreased extent, meaning that, should olefin/MA copolymersfunctionalized to the imide be desired, it is preferable to carry outthe reaction in the temperature range from about 50 to about 150° C.

[0024] The reactions to give the half-esters, half-amides and imides canbe carried out either without a diluent, or else in a solvent,preferably in the mineral oil used for formation of the explosiveemulsion. The latter is particularly preferred, in cases where theviscosity of the emulsifier permits it.

[0025] The emulsifiers according to the invention can be mixed with anycommon emulsifier. Preferred mixing components are the water-in-oilemulsifiers used in U.S. Pat. No. 3,447,978, such as sorbitanmonooleate, glycerides, phosphoric esters, etc., but alsoamidoamines/imidazolines obtainable by condensation of fatty acids withpolyamines. Particular preference is given to mixtures of theemulsifiers according to the invention with the monomeric emulsifiersspecified in EP-A-0 155 800 and EP-A-0 285 608, i.e. with derivatives ofalkenylsuccinic anhydrides, such as polyisobutenylsuccinic anhydride,i.e. half-esters, half-amides, imides and salts thereof with amines andalkali metals.

[0026] The emulsifiers according to the invention are suitable for useas constituent C in the explosive compositions (emulsion explosives) ofthe invention. The salt phase of the emulsion explosive (constituent A)consists of a supersaturated solution of an oxygen-releasing salt,ammonium nitrate preferably being used. Other oxygen-releasing salts,e.g. other nitrates such as sodium or potassium nitrate, and alsoperchlorates can also be used as additives.

[0027] The oil phase (constituent B) used is generally a mineral oil, inparticular a paraffin mineral oil. It is also possible to usenaphthene-based oils, vegetable oils, used oil or diesel oil. Theemulsifiers used are mostly predissolved in the oil phase. Theemulsifiers can be used as concentrate (up to 100% of active substance)or else as solution in a suitable oil, in cases where the inherentviscosity of the emulsifier is too high.

[0028] Further auxiliaries are bodying agents such as waxes, paraffinsor elastomers, in cases where the intention is to prepare cartridgedexplosive, products which are said to increase the water resistance ofthe emulsion, such as silicone oils, but also other emulsionstabilizers, thickeners or antioxidants, which are intended to preventaging of the emulsifier.

[0029] The explosive emulsion generally comprises 20-97% by weight,preferably 30-95% by weight, particularly preferably 70-95% by weight,of the discontinuous phase (i.e. predominantly water and ammoniumnitrate with the other water-soluble additives), and the water contentvaries in the range 2-30%, preferably in the range 4-20%. The oil phase(including the additives dissolved therein) includes about 1-20% byweight of the overall composition, but preferably 1-10%. The content ofemulsifier in the overall composition is in the range 0.2-5% by weight,preferably in the range 0.4-3%.

[0030] The explosive emulsions are preferably prepared using commonemulsifying processes. Firstly, a supersaturated ammonium nitratesolution (optionally with the addition of other water-solubleauxiliaries listed above) at 80-100° C. is prepared and heated until allsolids are dissolved, and, if necessary, the solution is filtered toremove insoluble material. In parallel, a solution of the emulsifier inthe oil matrix (likewise with the addition of other oil-solubleauxiliaries such as waxes, paraffins, antioxidants etc.), likewise at50-100° C., is prepared. Then, with stirring, the salt melt ispreferably added to the oil/emulsifier mixture, but the reverseprocedure is also possible. Vigorous stirring increases emulsionformation. The entrainment of seed crystals into the emulsion must beavoided. Where appropriate, other components, such as microballoons(glass bubbles), solids such as TNT, solid fuels such as aluminum orsulfur, inert materials such as baryte or sodium chloride, orundissolved ammonium nitrate are then added, and the mixture is stirreduntil the solids are distributed homogeneously. Chemical gassinginvolves adding, for example, thiourea and sodium nitrite, which leadsto gassing of the emulsion within a certain period. In industry, theemulsification stage can be carried out in special mixers and, whereappropriate, using static mixers.

[0031] The invention further provides a terpolymer comprising monomerunits derived from

[0032] A) an olefin having more than 40 carbon atoms,

[0033] B) maleic anhydride, and

[0034] C) an alkylallyl polyglycol ether of the formula

R—(OCH₂CH₂)_(n)O—CH₂—CH═CH₂

[0035] where n=3-20 and R=C₁-C₄-alkyl.

[0036] The olefin preferably has from 40 to 500, in particular from 40to 200, carbon atoms. It is preferably an α-olefin, particularlypreferably a polyisobutene. A particularly preferred embodiment relatesto modified terpolymers obtained by polymer-analogous reaction of thesaid terpolymers with alcohols, amines and aminoalcohols. Theterpolymers according to the invention are used as emulsifiers inexplosive compositions.

[0037] Particularly preferred terpolymers comprise monomer units of

[0038] A) 18 to 70 mol % of polyisobutene

[0039] B) 25 to 80 mol % of maleic anhydride

[0040] C) 2 to 15 mol % of allyl polyglycol ether.

[0041] As the experimental examples listed below demonstrate, thepolymeric emulsifiers according to the invention, alone or in particularin a mixture with other emulsifiers, such as, for example, sorbitanesters, exhibit identical emulsion stabilities to a conventionalpolyisobutenylsuccinic acid derivative. It is interesting that thefunctionalization of the polymeric anhydride, at least in mixtures withother emulsifiers, is not absolutely necessary. Under the conditions ofthe emulsification, the corresponding amide presumably forms from theanhydride and ammonium nitrate in situ.

EXAMPLES

[0042] Synthesis of the Polymeric Emulsifier

Example 1 Copolymer of Maleic Anhydride and Polyisobutylene

[0043] A 2 l four-necked flask fitted with a stirrer was charged with900 g (0.90 mol) of a polyisobutylene with a molecular weight of 1000g/mol and 88.2 g (0.90 mol) of maleic anhydride; the charge was heatedto 100° C. The system was then evacuated 3×up to 100 mbar and aerated ineach case with nitrogen in order to render it inert. The contents wereheated to 115° C. and 9.9 g (1% by weight) of di-tert-butyl peroxidewere added. The reaction mixture was heated further to 150° C., and thereaction temperature increased briefly to 160° C. The system was thenmaintained for 4 h at 150° C. Then, at 150° C., a reduced pressure of 20mbar was applied, although no distillate was obtained. Cooling gave 986g of a yellowish oil with a viscosity of 4.1 Pas at 80° C. (Bohlin, 10s⁻¹).

[0044] Molecular weight (GPC): Mn=1608 g/mol, Mw=3621 g/mol

[0045] Residual olefin content: 48%

Example 2 Copolymer of Maleic Anhydride, Polyisobutylene andC₁₈-α-Olefin

[0046] A 1 l four-necked flask fitted with stirrer was charged with 600g (0.60 mol) of a polyisobutylene with a molecular weight of 1000 g/mol,50 g (0.2 mol) of a C₁₈-α-olefin and 78.4 g (0.80 mol) of maleicanhydride; the contents were heated to 100° C. The system was thenevacuated 3×up to 100 mbar and aerated each time with nitrogen to renderit inert. The contents were heated to 120° C., and 7.3 g (1% by weight)of di-tert-butyl peroxide were added. The reaction mixture was heatedagain to 150° C., and the reaction temperature increased briefly to 160°C. The system was then maintained for 4 h at 150° C. Then, at 150° C., areduced pressure of 20 mbar was applied, although no distillate wasobtained. Cooling gave 725.8 g of an orange-red oil with a viscosity of4.0 Pas at 80° C. (Bohlin, 10 s⁻¹).

Example 3 Copolymer of Maleic Anhydride, Polyisobutylene and AllylmethylPolyglycol Ether With a Molecular Weight of 334 g/mol

[0047] A 2 l four-necked flask fitted with stirrer was charged with 1200g (1.20 mol) of a polyisobutylene with a molecular weight of 1000 g/mol,133.6 g (0.4 mol) of allylmethyl polyglycol ether and 156.8 g (1.60 mol)of maleic anhydride; the contents were heated to 100° C. The system wasthen evacuated 3×up to 100 mbar and aerated each time with nitrogen torender it inert. The contents were heated to 120° C., and 14.9 g (1% byweight) of di-tert-butyl peroxide were added. The reaction mixture wasagain heated to 150° C., and the reaction temperature increased brieflyto 155° C. The system was then maintained for 4 h at 150° C. Then, at150° C., a reduced pressure of 30 mbar was applied, and 4.0 g ofdistillate were obtained. Cooling gave 1469.6 g of a yellowish oil witha viscosity of 3.6 Pas at 80° C. (Bohlin, 10 s⁻¹).

[0048] Molecular weight (GPC): Mn=1540 g/mol, Mw=3460 g/mol

[0049] Residual olefin content: 52%

Example 4 Reaction of Example 1 With Diethylaminoethanol

[0050] A 2 l four-necked flask fitted with stirrer was charged with 312g of a paraffinic mineral oil and 657 g of the copolymer from Example 1;the contents were heated to 90° C. Over the course of 10 min, 70.3 g(0.6 mol) of N,N-diethylethanolamine were added dropwise, and themixture was stirred for 5 h at 90° C. This gave 1036 g of a yellow oil.

Example 5 Reaction of Example 2 With Diethylaminoethanol

[0051] A 2 l four-necked flask fitted with stirrer was charged with175.6 g of a paraffinic mineral oil and 362.9 g of the copolymer fromExample 2; the contents were heated to 90° C. Over the course of 10 min,46.9 g (0.4 mol) of N,N-diethylethanolamine were added dropwise, and themixture was stirred for 5 h at 90° C. This gave 582.4 g of a brown oil.

Example 6 Reaction of Example 3 With Diethylaminoethanol

[0052] A 2 l four-necked flask fitted with stirrer was charged with355.1 g of a paraffinic mineral oil and 734.8 g of the copolymer fromExample 3; the contents were heated to 90° C. Over the course of 10 min,93.8 g (0.6 mol) of N,N-diethylethanolamine were added dropwise, and themixture was stirred for 5 h at 90° C. This gave 1180.6 g of a red-brownoil.

Example 7 Comparative Example

[0053] This emulsifier was obtained by reacting apolyisobutyenylsuccinic anhydride (molecular weight of the parentpolyisobutene: 950 g/mol) with one mole equivalent of2-diethylaminoethanol at 90° C.

Example 8 Comparative Example

[0054] The comparative emulsifier used was a commercially availablesorbitan monooleate.

Example 9 Comparative Example

[0055] This emulsifier was obtained by condensation of tall oil fattyacid and triethylenetetramine in the molar ratio 3:1 at 230° C. and at areduced pressure of 20 mbar.

Example 10

[0056] The emulsifier of Example 4 was mixed in the mass ratio 80:20(taking into consideration the active substance content) with thecomparative emulsifier of Example 7 and homogenized at 60° C.

Example 11

[0057] The emulsifier of Example 4 was mixed in the mass ratio 80:20(taking into consideration the active substance content) with thecomparative emulsifier of Example 8 and homogenized at 60° C.

Example 12

[0058] The emulsifier of Example 4 was mixed in the mass ratio 50:50(taking into consideration the active substance content) with thecomparative emulsifier of Example 7 and homogenized at 60° C.

Example 13

[0059] The emulsifier of Example 1 was mixed in the mass ratio 50:50(taking into consideration the active substance content).with thecomparative emulsifier of Example 7 and homogenized at 60° C.

Example 14

[0060] The emulsifier of Example 5 was mixed in the mass ratio 50:50(taking into consideration the active substance content) with thecomparative emulsifier of Example 7 and homogenized at 60° C.

Example 15

[0061] The emulsifier of Example 6 was mixed in the mass ratio 50:50(taking into consideration the active substance content) with thecomparative emulsifier of Example 7 and homogenized at 60° C.

Example 16

[0062] The emulsifier of Example 4 was mixed in the mass ratio 90:10(taking into consideration the active substance content) with thecomparative emulsifier of Example 8 and homogenized at 60° C.

Example 17

[0063] The emulsifier of Example 4 was mixed in the mass ratio 90:10(taking into consideration the active substance content) with thecomparative emulsifier of Example 7 and homogenized at 60° C.

Example 18

[0064] Copolymer of Maleic Anhydride and Polyisobutene:

[0065] A 2 l four-necked flask fitted with stirrer was charged, under anitrogen atmosphere, with 700 g (0.70 mol) of a polyisobutylene with amolecular weight of 1000 g/mol, 500 g of 1,2-dichloroethane, 68.6 g(0.70 mol) of maleic anhydride and 7.7 g of tert-butyl perbenzoate; thecontents were heated to 80° C. The reaction mixture was in the form of aclear solution. The system was then maintained for 33 h at 80° C. Then,at 150° C. and a maximum reduced pressure of 20 mbar, 1,2-dichloroethaneand excess maleic anhydride were distilled off. Cooling gave 745 g of ayellowish, high-viscosity oil.

[0066] Molecular weight (GPC): Mn=1949 g/mol, Mw=5081 g/mol.

[0067] Residual olefin content: 66%

Example 19

[0068] Copolymer of Maleic Anhydride and Polyisobutene:

[0069] A 2 l four-necked flask fitted with stirrer was charged, under anitrogen atmosphere, with 800 g (0.80 mol) of a polyisobutylene with amolecular weight of 1000 g/mol, 545 g of xylene, 78.4 g (0.80 mol) ofmaleic anhydride and 8.8 g of tert-butyl perbenzoate; the contents wereheated to 80° C. The reaction mixture was in the form of a clearsolution. The system was then maintained for 30 h at 80° C. Then, at amaximum of 200° C. and a maximum reduced pressure of 20 mbar, xylene andexcess maleic anhydride were distilled off. Cooling gave 869 g of ayellowish, high-viscosity oil.

[0070] Molecular weight (GPC): Mn=1820 g/mol, Mw=4520 g/mol

[0071] Residual olefin content: 56%

Example 20

[0072] Copolymer of Maleic Anhydride and Polyisobutene:

[0073] A 2 l four-necked flask fitted with stirrer was charged with 1000g (1.00 mol) of a polyisobutylene with a molecular weight of 1000 g/mol,127.4 g (1.30 mol) of maleic anhydride and 538 g of xylene; the contentswere heated to 100° C., and the system was rendered inert by evacuating3×up to a reduced pressure of 300 mbar and aerating with nitrogen. At120° C., 11.3 g of di-tert-butyl peroxide were then added over thecourse of 5 min, and the reaction mixture was heated to 145° C.(reflux). The system was then maintained for 4 h at this temperature.Then, at a maximum of 200° C. and a maximum reduced pressure of 20 mbar,xylene and excess maleic anhydride were distilled off. Cooling gave 1137g of a yellowish, high-viscosity oil.

[0074] Molecular weight (GPC): Mn=1352 g/mol, Mw=2520 g/mol

[0075] Residual olefin content: 38.5%

Example 21

[0076] Reaction of Example 18 With Diethylethanolamine:

[0077] A 1 l four-necked flask fitted with stirrer was charged with 270g of a paraffinic mineral oil and 571 g of the copolymer of Example 18;the contents were heated to 90° C. Over the course of 10 min, 58.6 g(0.5 mol) of N,N-diethylethanolamine were added dropwise, and themixture was stirred for 5 h at 90° C. This gave 896 g of a yellow oil.

Example 22

[0078] Reaction of Example 19 With Diethylethanolamine:

[0079] A 2 l four-necked flask fitted with stirrer was charged with 305g of a paraffinic mineral oil and 654 g of the copolymer from Example19; the contents were heated to 90° C. Over the course of 10 min, 58.6 g(0.5 mol) of N,N-diethylethanolamine were added dropwise, and themixture was stirred for 5 h at 90° C. This gave 1015 g of a yellow oil.

Example 23

[0080] Reaction of Example 20 With Diethylethanolamine:

[0081] A 1 l four-necked flask fitted with stirrer was charged with 212g of a paraffinic mineral oil and 437 g of the copolymer from Example20; the contents were heated to 90° C. Over the course of 10 min, 58.6 g(0.5 mol) of N,N-diethylethanolamine were added dropwise, and themixture was stirred for 5 h at 90° C. This gave 701 g of a yellow, clearoil.

Example 24

[0082] The emulsifier of Example 21 was mixed in the mass ratio 50:50with the comparative emulsifier of Example 7 and homogenized at 60° C.

Example 25

[0083] The emulsifier of Example 22 was mixed in the mass ratio 50:50with the comparative emulsifier of Example 7 and homogenized at 60° C.

Example 26

[0084] The emulsifier of Example 23 was mixed in the mass ratio 50:50with the comparative emulsifier of Example 7 and homogenized at 60° C.

[0085] Determination of the molecular weights of the base polymers(Examples 1-3, 18-20):The molecular weights were determined by gelpermeation chromatography (GPC) using tetrahydrofuran as eluent againstpolyisobutene as standard; the values given were for Mn and Mw. Themolecular weight determinations include the unreacted polyisobutenepresent in the polymeric anhydride. The actual molecular weights of thepolymeric anhydride are accordingly considerably higher.

[0086] Determination of the residual olefin content (Examples 1-3,18-20): About 5-10 g of the polymeric anhydrides were chromatographedover 100 g of silica gel 60 using pentane as the eluent. The residualolefin is eluted here with an RF value of about 0.9. The correspondingfractions were combined, the solvent was distilled off and the residuewas weighed.

[0087] Preparation of the Test Emulsion

[0088] The test emulsion used has the following composition:

[0089] 1.0 g of emulsifier (100% of active substance not taking intoconsideration the oil content)

[0090] 6.3 g of white oil

[0091] 81.0 g of ammonium nitrate

[0092] 12.0 g of water

[0093] The white oil together with the emulsifier is introduced at 80°C. into a tall 250 ml beaker and, with stirring using a stainless steelanchor stirrer which passes close to the wall and with an increasingstirring rate from 800 to 2000 rpm, the clear, hot ammoniumnitrate/water melt at a temperature of from 95 to 98° C. is introduced.The melt is initially added dropwise and then added in one portion over15 seconds from a narrow-necked 100 ml Erlenmeyer flask such that it canbe stirred in the center of the stirrer blade; the melt must notsolidify on the wall. The resulting, transparent emulsion is thenstirred at 80° C. for from 3 to 5 min and drawn off while still hot(without any crystals which may have formed).

[0094] Emulsion Stability

[0095] The shelf life of the prepared emulsions was investigated a) atroom temperature (about 20-25° C.) and also b) during storage atfluctuating temperatures (alternating in each case for 24 h at 0° C. and40° C.). The assessment was visual; the emulsion was no longer regardedas stable if seed crystals had visibly formed. Storage stability atStorage stability at fluctuating Polymer Mixing Emulsifier RT (d)temperatures (d) component Additive ratio Example 1 0 0 Example 2 0 0Example 3 0 0 Example 4 >30 2 Example 5 >30 2 Example 6 0 0 Example7 >30 >30 (Comp.) Example 8 6 4 (Comp.) Example 9 6 1 (Comp.) Example10 >30 >30 Example 4 Example 7 80:20 Example 11 >30 >30 Example 4Example 8 80:20 Example 12 >30 >30 Example 4 Example 7 50:50 Example13 >30 >30 Example 1 Example 7 50:50 Example 14 >30 >30 Example 5Example 7 50:50 Example 15 >30 >30 Example 6 Example 7 50:50 Example16 >30 >30 Example 4 Example 8 90:10 Example 17 >30 >30 Example 4Example 7 90:10 Example 24 >30 >30 Example Example 7 50:50 21 Example25 >30 >30 Example Example 7 50:50 22 Example 26 >30 >30 Example Example7 50:50 23

1. An explosive composition consisting of D) an oxygen-donatingconstituent, which forms a disperse phase, E) an organic constituent,which forms a dispersion phase, and F) at least one emulsifier, whereinthe emulsifier includes a copolymer comprising, in random or regularorder, structural units derived from maleic anhydride and from one ormore olefins having more than 40 carbon atoms, where the structuralunits derived from maleic anhydride have been modified by reaction withalcohols, aminoalcohols, ammonia or amines.
 2. An explosive compositionas claimed in claim 1, wherein the composition comprises an alternatingcopolymer of at least one olefin having ca. 40-500 carbon atoms andmaleic anhhydride which has been modified with a) alcohols, b)aminoalcohols, c) ammonia or d) amines.
 3. An explosive composition asclaimed in claim 1 wherein the olefin is a polymer of short-chainolefins having 2-6 carbon atoms.
 4. An explosive composition as claimedin claim 3, wherein the short-chain olefin is butene or a butene isomer.5. An explosive composition as claimed in claim 1, wherein the olefinused is a mixture of polyisobutylene and a C₁₀-C₃₀-α-olefin.
 6. Anexplosive composition as claimed in 1, wherein the copolymer comprisesan alkylallyl polyglycol ether having 3-20 ethylene oxide units asfurther comonomer.
 7. An explosive composition as claimed in claim 1,wherein the polymer of maleic anhydride and olefins is reacted with anaminoalcohol to give the half-ester or a salt of the half-ester.
 8. Anexplosive composition as claimed in claim 7, wherein the aminoalcohol is2-dimethylaminoethanol or 2-diethylaminoethanol.
 9. An explosivecomposition as claimed in 1, wherein the coemulsifier used is aderivative of an alkenylsuccinic anhydride.
 10. An explosive compositionas claimed in claim 9, wherein the derivative of an alkenylsuccinicanhydride is a derivative of a polyisobutenylsuccinic anhydride.
 11. Anexplosive composition as claimed in claim 1, wherein the coemulsifierused is a sorbitan ester, imidazolines, phosphoric ester or fatty acidester.
 12. A terpolymer comprising monomer units derived from A) anolefin having more than 40 carbon atoms, B) maleic anhydride, and C) analkylallyl polyglycol ether of the formula R—(OCH₂CH₂)_(n)O—CH₂—CH═CH₂where n=3-20 and R=C₁-C₄-alkyl.
 13. A terpolymer obtained bypolymer-analogous reaction of terpolymers as claimed in claim 12 withalcohols, amines, ammonia or aminoalcohols.